1,4-Dihydronaphthalene derivatives

ABSTRACT

2,3-thioepoxytetralin, poly(2,3-thioepoxytetralin) and bis-(1,4dihydronaphtho)(2,3-c; 2,3-f) 1,2,5-trithiepane.

United States Patent 1 Fenoglio 1 Dec. 2, 1975 l l 1,4-DIHYDRONAPI-ITl-IALENE DERIVATIVES [75] Inventor: David J. Fenoglio, Carol Stream, Ill.

[73] Assignee: Standard Oil Company, Chicago, Ill.

[22] Filed: Jan. 14, 1973 [21] Appl. No.: 432,996

[52] U.S. Cl. 260/79; 260/79.7; 260/327 E;

260/327 B [51] Int. Cl. C07D 327/00; C08G 75/00 [58] Field of Search 260/79.7, 79, 327 E, 327 B [56] References Cited UNITED STATES PATENTS 2,694,073 11/1954 Soloway 260/327 E 3,213,107 10/1 65 Bremmer 260/327 E 3,260,755 7/1966 McNelis 260/79 3,347,867 10/1967 Osborn ct a1. 260/327 E 3,509,112 4/1970 Cameron 260/79 3,639,612 2/1972 De Long et a1. 260/327 B 3,699,020 10/1972 Connolly et al 204/73 R 3,723,417 3/1973 Perez-Alberne 260/327 B Primary Examiner-Ronald W. Griffin Attorney, Agent, or FirmWilliam H. Magidson; Arthur G. Gilkes; William T. McClain [5 7] ABSTRACT 2,3-thi0epoxytetralin, p0ly(2,3-thioepoxytetralin) and bis-(l,4-dihydronaphtho)[2,3-c; 2,3-f] 1,2,5- trithiepane.

3 Claims, No Drawings 1,4-DIHYDRONAPHTHALENE DERIVATIVES This invention relates to 2,3-thioepoxytetralin and derivative thereof.

In commonly assigned US. Pat. No. 3,699,020, there is disclosed an efficient electrochemical method of producing 1,4-dihydronaphthalene. The general object of this invention is to provide useful new compounds and polymers based on 1,4-dihydronaphthalene. A more specific object of this invention is to provide useful sulfur compounds and polymers based on 1,4-dihydronaphthalene. Other objects appear hereinafter.

In one aspect this invention is directed to 2,3-thioepoxytetralin.

In a second aspect this invention is directed to poly(2,3-thioepoxytetralin).

In a third aspect this invention is directed to Bis-(1,4- dihydronaphtho) [2,3-c; 2,3-f] 1,2,5-trithiepane.

I have now found that epoxidized l,4-dihydronaph thalene can be converted into 2,3-thioepoxytetralin. Biological testing has shown that this compound exhibited necrosis to fall pancium, jimsonweed and moderate retardation to pigweed and wild morningglory weed. The 2,3-thioepoxytetralin can be polymerized to form poly(2,3-thioepoxytetralin) which can be used as fibers, adhesives, surface active agents, etc. or converted to Bis-(1,4-dihydronaphtho) [2,3-c; 2,3-f] 1,2,5 -trithiepane. The latter compound can be used to control mexican bean beetle.

Briefly, 2,3-thioepoxytetralin can be prepared by reacting 2,3-epoxytetralin with a thiocyanate.

In somewhat greater detail, 2,3-thioepoxytetralin can be prepared by reacting 2,3-epoxytetralin with a thiocyanate, such as sodium or potassium thiocyanate, in an aqueous alcoholic medium under ambient conditions. Any water miscible alcohol can be used, such as methanol, ethanol, isopropanol, etc. Generally, the alcohol comprises 40 to 80% by weight of the aqueous alcohol medium. As the dissolved 2,3-epoxytetralin reacts and forms thioepoxytetralin, the thioepoxytetralin precipitates from the reaction medium.

The 2,3-thioepoxytetralin can be homopolymerized or copolymerized to polysulfides having a molecular weight of 10,000 to 25,000 or more by reacting the 2,3- thioepoxytetralin in a suitable solvent using a suitable polymerization catalyst. Suitable comonomers include ethylene oxide, ethylene episulfide, propylene oxide, propylene episulfide, 2,3-epoxytetralin, etc. For example, 2,3-thioepoxytetralin can be polymerized in a halohydrocarbon, such as methylene dichloride, 1,1,l-trichloroethane, etc. under nitrogen using either BF etherate or stannic chloride.

Although poly(2,3-thioepoxytetralin) can be produced by polymerizing 2,3-thioepoxytetralin at C. using stannic chloride catalyst, lower temperatures (about 70C.) are required for the BE, etherate catalyst. At 0 C., using BF}, etherate catalyst, bis-(1,4-dihydronaphtho) [2,3-c; 2,3-f]l,2,5-trithiepane is produced.

The poly (2,3-thioepoxytetralin) and poly (2,3-epoxytetralin) of Rothrock US. Pat. No. 2,054,099 can be chain extended by reaction with diisocyanates, such as toluene diisocyanate, to increase the polymer molecular weight. The chain extended polymers or the base polymers can be used to form fibers or as adhesives.

The following examples are merely illustrative.

EXAMPLE 1 Twenty and one-half grams 2,3-epoxytetralin, ml ethanol, 19.4 grams potassium thiocyanate and 50 ml water were stirred for 5 days at room temperature in a 250 ml-Erlynmeyer flask equipped with a magnetic stirrer. The mixture was filtered, washed with water and a white solid collected. The filtrate was stirred at room temperature for six more days, filtered, washed with water and a white solid combined with the first crop of solids, which had a combined weight of 14.65 grams (65% yield). After recrystallization from ethyl ether, the 2,3-thioepoxytetralin melted at 73 C. The nmr, IR and analytical data were all consistent with 2,3-thioepoxytetralin.

Theory Found Carbon 74.03 74.28

Hydrogen 6.21 6.16

EXAMPLE II One and forty-three one-hundredths grams 2,3-thioepoxytetralin, 5 ml of methylene dichloride and 0.056 ml BF; etherate were placed in a vial under nitrogen and sealed. After standing at 0C. for 24 hours, 0.8 grams of crystals were filtered off. The product was recrystallized from benzene and melted at l89-l90 C. Mass spectrum and chemical analysis indicated that the compound was bis-(1,4-dihydronaphtho) [2,3-c; 2,3-f] l ,2,5-trithiepane.

Theory Actual Carbon 67.37 68.01 Hydrogen 5.65 5.67 Sulfur 26.98 26.1 1

EXAMPLE Ill EXAMPLE IV Example III was repeated using varying concentrations of stannic chloride catalyst in place of the BF, etherate and 0 C. reaction temperature. The results are set forth below in Table I.

Table I moles Stannic Chloride Molecular based on thioepoxide Weight of Polymer Yield Table l-continued moles Stannic Chloride based on thioepoxide Molecular Weight of Polymer form of a homopolymer. 

1. 2,3-THIOEPOXYTETRALIN.
 2. POLY(2,3-THIOEPOXYTETRALIN).
 3. The poly (2,3-thioepoxytetralin) of claim 2 in the form of a homopolymer. 